CN104498027A - Fluorescent powder high in luminous efficacy and heat stability and preparation method of fluorescent powder - Google Patents

Fluorescent powder high in luminous efficacy and heat stability and preparation method of fluorescent powder Download PDF

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Publication number
CN104498027A
CN104498027A CN201410706271.9A CN201410706271A CN104498027A CN 104498027 A CN104498027 A CN 104498027A CN 201410706271 A CN201410706271 A CN 201410706271A CN 104498027 A CN104498027 A CN 104498027A
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China
Prior art keywords
powder
fluorescent material
fluorescent powder
preparation
thermal stability
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CN201410706271.9A
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Chinese (zh)
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刘志刚
武东亮
刘红
曾令贤
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GUANGZHOU ZHUJIANG PHOTOELECTRIC NEW MATERIALS Co Ltd
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GUANGZHOU ZHUJIANG PHOTOELECTRIC NEW MATERIALS Co Ltd
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Abstract

The invention provides fluorescent powder high in luminous efficacy and heat stability. The fluorescent powder is blue fluorescent powder; the chemical molecular formula of the fluorescent powder is Mg1BaxSr1-x-yAl10O17: Euy, wherein y is greater than or equal to 0.10 and less than or equal to 0.30. Activated carbon blocks are put into a crucible and continuously pushed into an electrical furnace at a temperature ranging from 1300 to 1600 DEG C for primary reduction in the presence of N2; and besides, the activated carbon blocks are continuously pushed into electrical furnace at a temperature ranging from 1300 to 1600 DEG C for secondary reduction in the presence of the mixed gases of N2 and H2. The unimodal blue fluorescent powder (Mg1BaxSr1-x-yAl10O17: Euy, wherein y is greater than or equal to 0.10 and less than or equal to 0.30) which is high in luminous efficacy and heat stability and high in europium content is prepared by use of a unique secondary reduction process; as the content of the europium element in the powder is increased, the luminous efficacy of the blue fluorescent powder is increased by 20-30%. The illuminant color offset problem of the high-europium content fluorescent powder is solved; and meanwhile, the heat stability of the powder is obviously improved and the anti-thermal degradation property of the powder is increased by more than 20%.

Description

A kind of specular removal, high thermal stability fluorescent material and preparation method thereof
Technical field
The present invention relates to rare earth luminescent material preparing technical field, be specifically related to a kind of specular removal, high thermal stability fluorescent material and preparation method thereof.
Background technology
In three primary colors fluorescent powder, comparing rouge and powder and green powder, there is the problems such as light efficiency is low, light decay is large due to its reason such as crystalline structure, preparation technology in BAM aluminate blue fluorescent powder.The thermal degradation when of BAM blue colour fluorescent powder in luminescent lamp making processes is the major cause causing luminescent lamp light decay; Although by increasing the europium constituent content in fluorescent material, can to a certain degree improve fluorescent material light efficiency; But along with content increases, europium element reduction becomes more difficult, the blue powder illuminant colour offset problem of high europium content is more obvious, and above problem seriously restricts the synthesis of high-quality BAM blue powder.
Summary of the invention
Object of the present invention is exactly solve the not high shortcoming of existing blue colour fluorescent powder luminous efficiency, provides a kind of specular removal, high thermal stability fluorescent material and preparation method thereof
One of goal of the invention of the present invention is realized by following proposal:
A kind of specular removal, high thermal stability fluorescent material, described fluorescent material is blue colour fluorescent powder, and its chemical molecular formula is: Mg 1ba xsr 1-x-yal 10o 17: Eu y, wherein 0.10≤y≤0.30.
Another goal of the invention of the present invention is realized by following proposal:
A preparation method for specular removal, high thermal stability fluorescent material, comprises the following steps:
Step one ,be in harmonious proportion:
According to molecular formula Mg 1ba xsr 1-x-yal 10o 17: Eu ystoichiometrically than weighing, after mixing, taking appropriate powder and loading corundum crucible.
Step 2, to burn till:
A: place activated carbon block in crucible, at the 1300-1600 DEG C of electric stove N of continuous pushing type 2once reduce under condition, wherein at 1300-1600 DEG C of interval stop 2-5 hour, whole firing period is 30 hours;
B: take out powder, powder is broken;
C: take the rear powder of appropriate pulverizing, load corundum crucible, carry out secondary reduction under 1300-1600 DEG C of continuous pushing type electric stove N2+H2 mixed gas condition, wherein stop 2-5 hour in 1300-1600 DEG C of interval, whole firing period is 30 hours.
Step 3, process:
Burning till powder adopts wet ball grinding technique to process, and powder and appropriate pure water are mixed to form suspension liquid, and the ball-milling dispersion machine of abrading-ball is equipped with in rear injection; Obtain the fluorescent material powder of appropriate particle size by controlling Ball-milling Time under certain speed conditions.
Step 4, cleaning, dehydration, drying:
Cleaned by fluorescent material suspension liquid pure water, clean to specific conductivity≤10 μ s/cm, adopt centrifuge dehydration, powder is dry under 100-150 DEG C of condition, namely obtains unimodal blue colour fluorescent powder after drying completes.
Wherein, in described step one, aluminum oxide oikocryst type is α-Al 2o 3, granularity is 2-8 μm, purity>=99.5%.
Wherein, in described step one, barium compound, strontium compound all adopt purity >=99.5% carbonate.
Wherein, in described step one, magnesium compound adopts purity >=99.5% magnesium oxide.
Wherein, in described step one, europium compound adopts the europium sesquioxide of purity >=99.99%.
Wherein, in described step one, fusing assistant adopts one or more mixing in barium fluoride, magnesium fluoride, aluminum fluoride, boric acid, ammonium chloride, and flux content controls at 0.05%-5.00%.
This patent adopts secondary reduction method successfully to prepare high europium content (Mg 1ba xsr 1-x-yal 10o 17: Eu y, 0.10≤y≤0.30) and BAM blue colour fluorescent powder, by improving europium constituent content, the light efficiency of blue colour fluorescent powder improves 20-30%.By the improvement to fusing assistant formula and production technique, europium element is reduced sufficiently in preparation process, solves high europium content light-emitting phosphor color shift problem; Simultaneously powder thermostability be improved significantly, anti-thermal degradation effect improves more than 20%.
Embodiment
embodiment1
A preparation method for specular removal, high thermal stability fluorescent material, comprises the following steps:
Step one, mediation:
According to molecular formula Mg 1ba xsr 1-x-yal 10o 17: Eu ystoichiometrically than weighing, after mixing, taking appropriate powder and loading corundum crucible.
Aluminum oxide oikocryst type is α-Al 2o 3, granularity is 2-8 μm, purity>=99.5%.
Barium compound, strontium compound all adopt purity >=99.5% carbonate.
Magnesium compound adopts purity >=99.5% magnesium oxide.
Europium compound adopts the europium sesquioxide of purity >=99.99%.
Fusing assistant adopts barium fluoride, magnesium fluoride, aluminum fluoride, boric acid, in ammonium chloride one or more, flux content is 0.05%.
Step 2, to burn till:
A: place activated carbon block in crucible, at 1500 DEG C of electric stove N of continuous pushing type 2once reduce under condition, wherein stop 2 hours at 1500 DEG C, whole firing period is 30 hours;
B: take out powder, powder is broken;
C: take the powder that appropriate pulverizing is enough, load corundum crucible, at 1500 DEG C of high temperature firing furnace N 2+ H 2carry out secondary reduction under mixed gas protected condition, wherein 1500 DEG C of interval stops 2 hours, whole firing period is 30 hours.
Step 3, process:
Burning till powder adopts wet ball grinding technique to process, and powder and appropriate pure water are mixed to form suspension liquid, and the ball-milling dispersion machine of abrading-ball is equipped with in rear injection; Obtain the fluorescent material powder of appropriate particle size by controlling Ball-milling Time under certain speed conditions.
Step 4, cleaning, dehydration, drying
Cleaned by fluorescent material suspension liquid pure water, clean to specific conductivity≤10 μ s/cm, adopt centrifuge dehydration, powder is dry under 100-150 DEG C of condition, namely obtains unimodal blue colour fluorescent powder after drying completes.
embodiment 2
A preparation method for specular removal, high thermal stability fluorescent material, comprises the following steps:
Step one, mediation:
According to molecular formula Mg 1ba xsr 1-x-yal 10o 17: Eu ystoichiometrically than weighing, after mixing, taking appropriate powder and loading corundum crucible.
Aluminum oxide oikocryst type is α-Al 2o3, granularity is 2-8 μm, purity>=99.5%.
Barium compound, strontium compound all adopt purity >=99.5% carbonate.
Magnesium compound adopts purity >=99.5% magnesium oxide.
Europium compound adopts the europium sesquioxide of purity >=99.99%.
Fusing assistant adopts barium fluoride, magnesium fluoride, aluminum fluoride, and flux content is 5.00%.
Step 2, to burn till:
A: place activated carbon block in crucible, once reduce under 1300 DEG C of high temperature firing furnace nitrogen protection conditions, wherein 1300 DEG C of interval stops 5 hours, whole firing period is 30 hours;
B: take out powder, powder is broken;
C: take the powder that appropriate pulverizing is enough, load corundum crucible, carry out secondary reduction under 1300 DEG C of high temperature firing furnace nitrogen and hydrogen gas mixture protective condition, wherein stop 5 hours at 1300 DEG C, whole firing period is 30 hours.
Step 3, process:
Burning till powder adopts wet ball grinding technique to process, and powder and appropriate pure water are mixed to form suspension liquid, and the ball-milling dispersion machine of abrading-ball is equipped with in rear injection; Obtain the fluorescent material powder of appropriate particle size by controlling Ball-milling Time under certain speed conditions.
Step 4, cleaning, dehydration, drying:
Cleaned by fluorescent material suspension liquid pure water, clean to specific conductivity≤10 μ s/cm, adopt centrifuge dehydration, powder is dry under 100-150 DEG C of condition, namely obtains unimodal blue colour fluorescent powder after drying completes.
embodiment 3
A preparation method for specular removal, high thermal stability fluorescent material, comprises the following steps:
Step one, mediation:
According to molecular formula Mg 1ba xsr 1-x-yal 10o 17: Eu ystoichiometrically than weighing, after mixing, taking appropriate powder and loading corundum crucible.
Aluminum oxide oikocryst type is α-Al 2o 3, granularity is 2-8 μm, purity>=99.5%.
Barium compound, strontium compound all adopt purity >=99.5% carbonate.
Magnesium compound adopts purity >=99.5% magnesium oxide.
Europium compound adopts the europium sesquioxide of purity >=99.99%.
Fusing assistant adopts aluminum fluoride, and flux content is 0.05%.
Step 2, to burn till:
A: place activated carbon block in crucible, at 1450 DEG C of electric stove N of continuous pushing type 2once reduce under condition, wherein 1450 DEG C of interval stops 3 hours, whole firing period is 30 hours;
B: take out powder, powder is broken;
C: take the powder that appropriate pulverizing is enough, load corundum crucible, at 1400 DEG C of electric stove N of continuous pushing type 2+ H 2carry out secondary reduction under nitrogen and hydrogen gas mixture protective condition, wherein 1400 DEG C of interval stops 4 hours, whole firing period is 30 hours.
Step 3, process:
Burning till powder adopts wet ball grinding technique to process, and powder and appropriate pure water are mixed to form suspension liquid, and the ball-milling dispersion machine of abrading-ball is equipped with in rear injection; Obtain the fluorescent material powder of appropriate particle size by controlling Ball-milling Time under certain speed conditions.
Step 4, cleaning, dehydration, drying:
Cleaned by fluorescent material suspension liquid pure water, clean to specific conductivity≤10 μ s/cm, adopt centrifuge dehydration, powder is dry under 100-150 DEG C of condition, namely obtains unimodal blue colour fluorescent powder after drying completes.
Powder thermostability and thermal degradation when experiment:
In order to prepare the high powder of thermostability more meeting luminescent lamp coating, we adopt fluorescent material in above embodiment to carry out thermostability and thermal degradation when characteristic test:
A: take appropriate fluorescent material and put into alumina crucible;
B: crucible is put into ceramic saggar stand-by;
C: under air conditions, retort furnace is warmed up to 800 DEG C, puts into retort furnace by ceramic saggar and keeps certain hour, takes out saggar and is cooled to room temperature;
D: illuminant colour and relative brightness change before measuring fluorescent material calcination respectively with spectrograph, after calcination, carries out powder Evaluation of Thermal Stability with this.
Unimodal blue colour fluorescent powder (the Mg of high europium content that this patent adopts unique secondary reduction technique to prepare, and light efficiency is high, heat setting is good 1ba xsr 1-x-yal 10o 17: Eu y, 0.10≤y≤0.30), by the raising of europium content, the light efficiency of blue colour fluorescent powder improves 20-30%.By the improvement to formula and production technique, europium element is reduced sufficiently in preparation process, solves high europium content light-emitting phosphor color shift problem; Simultaneously powder thermostability be improved significantly, anti-thermal degradation characteristic improves more than 20%.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention; although be explained in detail the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.

Claims (7)

1. specular removal, a high thermal stability fluorescent material, is characterized in that: described fluorescent material is blue colour fluorescent powder, and its chemical molecular formula is: Mg 1ba xsr 1-x-yal 10o 17: Eu y, wherein 0.10≤y≤0.30.
2. the preparation method of a kind of specular removal according to claim 1, high thermal stability fluorescent material, comprises the following steps:
Step one, mediation:
According to molecular formula Mg 1ba xsr 1-x-yal 10o 17: Eu y, stoichiometrically than weighing, after mixing, taking appropriate powder and loading corundum crucible.
Step 2, to burn till:
A: place activated carbon block in crucible, advances electric stove N continuously at 1300-1600 DEG C 2once reduce under protective condition, wherein at 1300-1600 DEG C of interval stop 2-5 hour, whole firing period is 30 hours;
B: take out powder, powder is broken;
C: take the rear powder of appropriate pulverizing, load corundum crucible, advance electric stove N continuously at 1300-1600 DEG C 2+ H 2carry out secondary reduction under mixed gas condition, wherein at 1300-1600 DEG C of interval stop 2-5 hour, whole firing period is 30 hours.
Step 3, process:
Burning till powder adopts wet ball grinding technique to process, and powder and appropriate pure water are mixed to form suspension liquid, after the ball-milling dispersion machine of abrading-ball suspension liquid injection is equipped with; Under certain ball milling rate conditions, obtain the fluorescent material powder of appropriate particle size by controlling Ball-milling Time.
Step 4, cleaning, dehydration, drying:
Cleaned by fluorescent material suspension liquid pure water, clean to specific conductivity≤10 μ s/cm, adopt centrifuge dehydration, powder is dry under 100-150 DEG C of condition, namely obtains unimodal blue colour fluorescent powder after drying completes.
3. the preparation method of a kind of specular removal according to claim 2, high thermal stability fluorescent material, is characterized in that: in described step one, aluminum oxide oikocryst type is α-Al 2o 3, granularity is 2-8 μm, purity>=99.5%.
4. the preparation method of a kind of specular removal according to claim 2, high thermal stability fluorescent material, is characterized in that: in described step one, barium compound, strontium compound all adopt purity >=99.5% carbonate.
5. the preparation method of a kind of specular removal according to claim 2, high thermal stability fluorescent material, is characterized in that: in described step one, and magnesium compound adopts purity >=99.5% magnesium oxide.
6. the preparation method of a kind of specular removal according to claim 2, high thermal stability fluorescent material, is characterized in that: in described step one, and europium compound adopts the europium sesquioxide of purity >=99.99%.
7. the preparation method of a kind of specular removal according to claim 2, high thermal stability fluorescent material, it is characterized in that: in described step one, fusing assistant adopts wherein one or more mixing in barium fluoride, magnesium fluoride, aluminum fluoride, boric acid, ammonium chloride, and flux content controls at 0.05%-5.00%.
CN201410706271.9A 2014-11-28 2014-11-28 Fluorescent powder high in luminous efficacy and heat stability and preparation method of fluorescent powder Pending CN104498027A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105043682A (en) * 2015-08-04 2015-11-11 浙江工商大学 Boiler leak detection system and method
CN115678541A (en) * 2022-09-29 2023-02-03 广州珠江光电新材料有限公司 High-performance special blue-green fluorescent powder and preparation method thereof
CN115785943A (en) * 2022-10-19 2023-03-14 广州珠江光电新材料有限公司 Blue-green fluorescent powder with core-shell structure and preparation method thereof
CN116575107A (en) * 2022-11-01 2023-08-11 广州珠江光电新材料有限公司 Preparation method of blue fluorescent powder, product and application thereof

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CN101914380A (en) * 2010-02-02 2010-12-15 湖南信多利新材料有限公司 Rare earth aluminate blue-green fluorescent powder and preparation method thereof

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Publication number Priority date Publication date Assignee Title
JP2000178552A (en) * 1998-12-14 2000-06-27 Toray Ind Inc Phosphor powder for display and phosphor paste
US20050275333A1 (en) * 2004-06-14 2005-12-15 Ru-Shi Liu White light illumination device and method of manufacturing the same
CN101717633A (en) * 2009-11-17 2010-06-02 江门市科恒实业股份有限公司 Preparation method of europium-activated aluminate blue fluorescent powder
CN101914380A (en) * 2010-02-02 2010-12-15 湖南信多利新材料有限公司 Rare earth aluminate blue-green fluorescent powder and preparation method thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105043682A (en) * 2015-08-04 2015-11-11 浙江工商大学 Boiler leak detection system and method
CN105043682B (en) * 2015-08-04 2018-11-02 浙江工商大学 boiler leak detection system and method
CN115678541A (en) * 2022-09-29 2023-02-03 广州珠江光电新材料有限公司 High-performance special blue-green fluorescent powder and preparation method thereof
CN115785943A (en) * 2022-10-19 2023-03-14 广州珠江光电新材料有限公司 Blue-green fluorescent powder with core-shell structure and preparation method thereof
CN115785943B (en) * 2022-10-19 2023-08-08 广州珠江光电新材料有限公司 Blue-green fluorescent powder with core-shell structure and preparation method thereof
CN116575107A (en) * 2022-11-01 2023-08-11 广州珠江光电新材料有限公司 Preparation method of blue fluorescent powder, product and application thereof

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